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Measurements of the rotational spectra of (sup 17)O(sup 16)O(sup 16)O and (sup 16)O(sup 17)O(sup 16)O have been extended to allow determination of a complete set of sextic centrifugal distortion constants for both molecules.
The first compound in the series of reactions leading to the ester conjugates of indole-3-acetic acid (IAA) in kernels of Zea mays sweet corn is the acyl alkyl acetal, 1-O-indol-3-ylacetyl-beta-D-glucose (1-O-IAGlu). The enzyme catalyzing the synthesis of this compound is UDP-glucose:indol-3-ylacetate glucosyl-transferase (IAGlu synthase). The IAA moiety of the high energy compound 1-O-IAGlu may be enzymatically transferred to myo-inositol or to glycerol or the 1-O-IAGlu may be enzymatically hydrolyzed. Alternatively, nonenzymatic acyl migration may occur to yield the 2-O, 4-O, and 6-O esters of IAA and glucose. The 4-O and 6-O esters may then be enzymatically hydrolyzed to yield free IAA and glucose. This work reports new enzymatic activities, the transfer of IAA from 1-O-IAGlu to glycerol, and the enzyme-catalyzed hydrolysis of 4-O and 6-O-IAGlu. Data is also presented on the rate of non-enzymatic acyl migration of IAA from the 1-O to the 4-O and 6-O positions of glucose. We also report that enzymes catalyzing the synthesis of 1-O-IAGlu and the hydrolysis of 1-O, 4-O, and 6-O-IAGlu fractionate as a hormone metabolizing complex. The association of synthetic and hydrolytic capabilities in enzymes which cofractionate may have physiological significance.
Experimental and theoretical excitation cross sections are reported for the first forbidden transition 4S(O) -- 2S(2)2p(3) 2D(O) (lambda-lambda 3726, 3729) and the first allowed (resonance) transition 4S(O) -- 2s2p(4) 4P(lambda-833) in O II. Use is made of electron energy loss and merged-beams methods. The electron energy range covered is 3.33 (threshold) to 15 eV for the S -- D transition, and 14.9 (threshold) to 40 eV for the S -- P transition. Care was taken to assess and minimize the metastable fraction of the O II beam. An electron mirror was designed and tested to reflect inelastically backscattered electrons into the forward direction to account for the full range of polar scattering angles. Comparisons are made between present experiments and 11-state R-matrix calculations. Calculations are also presented for the 4S(O) -- 2s(2)2p(3)2P(O) (lambda-2470) transition.
Potential energy curves for O - O interactions corresponding to the X (sup 3) Sigma - g, 1 delta g, 1 Sigma plus g, 3 delta u, A3 Sigma plus u, 1 Sigma - u, and B3 Sigma states of O (sub 2) have been calculated from spectroscopic data by the Rydberg‐Klein‐Rees method. Curves for the remaining twelve states of O (sub 2) dissociating to ground state atoms have been obtained from relations derived from approximate quantum‐mechanical calculations, and checked against the meager experimental information available. Two semi‐independent calculations have been made, and are in good agreement with each other. The quantum‐mechanical relations also lead to an approximate O (sub 2) - O (sub 2) interaction, which is consistent with interactions derived from vibrational relaxation times and from high‐temperature gas viscosity data.
Theoretical description of the reaction rate of an ion-molecule interchange reaction as a function of collision parameters
Thermionic work functions and desorption energies for oxygen on polycrystalline W, Mo and Re filaments, discussing oxygen pressure and filament temperature
Reaction rate constants of ion-molecule interchange reaction as function of temperature, flow velocity, activation energy and constant part of steric factor P
L profiles of ions with intermediate charge states (O(5+), O(4+), and O(3+) are presented and compared with those of O(+), O(2+), and O(6+) ions in order to determine their possible sources of origin. The L profiles exhibit broad maxima located at L = 6-7 for O(3+) and O(4+) and L = 7-8 for O(5+) ions during periods of low to medium geomagnetic activity. With increasing Kp, the flux versus L distributions extend further earthward and the maxima move to slightly lower L values. While the flux decrease earthward of the maximum is very steep, the gradual decrease outward of the maximum becomes flatter with increasing charge state. These results suggest that O(3+), O(4+), and O(5+) ions are produced predominantly by charge exchange processes, and that the O(4+) and O(5+) ions are produced from the solar wind-originating O(6+).
Measurements with the charge energy mass spectrometer of the AMPTE CCE spacecraft are used to determine the relative fluxes of these ions near the equatorial plane as a function of the drift shell parameter L, the magnetic activity index Kp, and the local time LT. The O(+) and O(2+) ions have radial profiles with maxima at about L = 5 and diurnal variations with a broad maximum on the dayside. The O(6+) and C(6+) ion fluxes increase with L between L = 5 and L = 7 and level off farther out. The diurnal variations of the relative O(6+) and C(6+) fluxes exhibit a pronounced minimum on the dayside. The observations can be interpreted in terms of ion convection from the tail onto quasi-trapped drift orbits and further radial diffusion onto closed drift shells. The maximum of the O(+) and O(2+) fluxes as well as the minimum of the O(6+) and C(6+) fluxes on the dayside can be explained by drift shell splitting. The inward transport is associated with ion losses, mainly by charge exchange. O(6+) and C(6+) ions are removed already at larger distances than O(+) and O(2+). As a result, the ionosphere contributes most of the oxygen ions in the magnetosphere. Important contributions from the solar wind are encountered in the outer magnetosphere.
Accurate collision integrals for the interactions of N(4S0) + N(4S0), O(3P) + O(3P), and N(4S0) + O(3P) are reported. These are computed from a semiclassical formulation of the scattering using the best available representations of all of the potential energy curves needed to describe the collisions. Spectroscopic curves and other accurate measured data are used where available; the results of accurate ab initio electronic structure calculations are used to determine the remaining potential curves. The high-lying states are found to give the largest contributions to the collision cross sections. The nine collision integrals needed to determine transport properties to second order are tabulated for translational temperatures in the range 250-100,000 K. The viscosity, thermal conductivity, diffusion coefficient, and thermal diffusion factor for a gas composed of nitrogen and oxygen atoms in thermal equilibrium have been calculated. It is found that the second-order contribution to the transport properties is small. Graphs of these transport properties for various mixture ratios are presented for temperatures in the range 5000-15,000 K.
Experimental and theoretical collisional excitation cross sections are reported for the transitions 3s(exp 2)3p(exp 3)4S(exp o) approaches 3s(exp 2)3p(exp 3) 2D(exp o), 2P(exp o), and 3s3P(exp 4) 4P in S II. The transition wavelengths (energies) are 6716 A (1.85 eV), 4069 A (3.05 eV), and 1256 A (9.87 eV), respectively. In the experiments, use is made of the energy-loss merged-beams method. The metastable fraction of the S II beam was assessed and minimized. The contribution of elastically scattered electrons was reduced by the use of a lowered solenoidal magnetic field and a modulated radio-frequency voltage on the analyzing plates and by retarding grids to reject the elastically scattered electrons with larger Larmor radii. For each transition, comparisons are made among experiments, the new 19 state R-matrix calculation, and three other close-coupling calculations.
Potential energy curves for 0-N interactions corresponding to the X (sup 2) II (sub t/2), X (sup 2) II (sub 3/2), A (sup 2) Eta (sup plus), B (sup 2) II, C (sup 2) II, D (sup 2) Eta (sup plus), E (sup 2) Eta (sup plus), and B prime (sup 2 delta) states of nitric oxide have been calculated from spectroscopic data by the Rydberg- Klein-Rees method. Curves for the (sup 4) II, (sup 2) Eta, (sup 4) Eta, (sup 6) Eta, and (sup 6) II states have been obtained from limited spectroscopic results and from relations derived from approximate quantum-mechanical calculations. Two semi-independent calculations have been made, and are in good agreement with each other. The quantum-mechanical relations also lead to approximate curves for the O[Single Bond]N, and O[Single Bond]N (sub 2) interactions over a limited range. The O (sub 2)[Single Bond]N (sub 2) interaction is consistent with one valid at larger separation distances which has been derived from high-temperature gas viscosity data.
Accurate collision integrals are reported for the interactions of N(4 S 0) + N(4 S 0), O(3 P), and N(4 S 0) + O(3 P). These are computed from a semiclassical formulation of the scattering using the best available representations of all of the potential energy curves needed to describe the collisions. Experimental RKR curves and other accurate measured data are used where available; the results of accurate ab initio electronic structure calculations are used to determine the remaining potential curves. The high-lying states are found to give the largest contributions to the collision cross sections. The nine collision integrals, needed to determine transport properties to second order, are tabulated for translational temperatures in the range 250 K to 100,000 K. These results are intended to reduce the uncertainty in future predictions of the transport properties of nonequilibrium air, particularly at high temperatures. The viscosity, thermal conductivity, diffusion coefficient, and thermal diffusion factor for a gas composed of nitrogen and oxygen atoms in thermal equilibrium are calculated. It was found that the second order contribution to the transport properties is small. Graphs of these transport properties for various mixture ratios are presented for temperatures in the range 5000 to 15000 K.
Measurements of line positions and strengths of D2 O-18 and HD O-18 were obtained with a Fourier transform spectrometer. The data were analyzed to obtain energy levels of the (100), (020), and (001) vibrational states of HD O-18 and the (001) and (011) states of D2 O-18 and the vibrational bands of these states connected to the ground state covered the spectral region from 2500 to 4278 cm(exp -1). 456 absorption lines of D2 O-18 and 856 lines of HD O-18 were assigned from the spectra. The measurements were of oxygen-18 enriched samples of deuterated water vapor and the spectra also contained features of HD O-16, D2 O-16, H2 O-16, H2 O-17 and H2 O-18 of which several were used as frequency calibration standards.
Stable oxygen isotopes measured in tree rings are useful for reconstructing climate variability and explaining changes in physiological processes occurring in forests, complementing other tree-ring parameters such as ring width. Here, we analyzed the relationships between different climate parameters and annually resolved tree-ring δ(18)O records (δ(18)O(TR)) from white spruce (Picea glauca [Moench]Voss) trees located near Tungsten (Northwest Territories, Canada) and used the NASA GISS ModelE2 isotopically-equipped general circulation model (GCM) to better interpret the observed relationships. We found that the δ(18)O(TR) series were primarily related to temperature variations in spring and summer, likely through temperature effects on the precipitation δ(18)O in spring, and evaporative enrichment at leaf level in summer. The GCM simulations showed significant positive relationships between modelled precipitation δ(18)O over the study region and surface temperature and geopotential height over northwestern North America, but of stronger magnitudes during fall-winter than during spring–summer. The modelled precipitation δ(18)O was only significantly associated with moisture transport during the fall-winter season. The δ(18)O(TR) showed similar correlation patterns to modelled precipitation δ(18)O only during spring–summer when water matters more for trees, with significant positive correlations with surface temperature and geopotential height, but no correlations with moisture transport. Overall, the δ(18)O(TR) records for northwestern Canada reflect the same significant large-scale climate patterns as precipitation δ(18)O for spring–summer, and therefore have potential for reconstructing past atmospheric dynamics in addition to temperature variability in the region.
The oxygen isotopic composition of the Sun inferred from the measurements of the solar wind returned by the Genesis spacecraft is O-16-enriched (△O-17 = -28.4±3.6‰) relative to the whole-rock O-isotope compositions of chondrites and achondrites, and chondrule phenocrysts, which all plot close to the terrestrial fractionation line (△O-17 ∼ ±5‰). Vast majority of refractory inclusions (CAIs and AOAs) in carbonaceous chondrites of petrologic types 2-3.0 are iso-topically uniform and have solar-like △O-17. In contrast, CAIs and AOAs in metamorphosed CV and CO chondrites are isotopically heterogeneous with melilite, anorthite, perovskite, Zr- and Sc-rich oxides and silicates, and occasionally Al, Ti-diopside being O-16-depleted relative to hibonite, spinel, Al-diopside, and forsterite. The timing of generation of different O-isotope reservoirs and the nature of O-isotope heterogeneity in refractory inclusions in CO3 and CV3 chondrites are poorly known. Grossite (CaAl4O7) is one of the first minerals predicted to condense from a gas of solar composition and therefore it could have recorded isotopic compositions of reservoirs during the earliest stages of the Solar System evolution. Here we report on O-isotope compositions of grossite-rich CAIs in CH3 and CO3 chondrites measured in situ with the UH Cameca ims-1280. For analytical procedures see [9].
Measurements of the absorptions in the Venus atmosphere by (C-12)O and (C-13)O in the J = 1-2 microwave, rotational transitions are reported. Radiative transfer models were fitted to the spectra in order to estimate the isotopic ratio (C-12)O/(C-13)O = 185. Based on an extensive error analysis it is suggested that the standard deviation of this value is + or - 69. This result applies to the mesosphere of Venus, i.e., from about 80 to 110 km. Values of the (C-12)O/(C-13)O ratio measured deeper in the Venus atmosphere are closer to the terrestrial value of 89. Several possible, qualitative mechanisms to explain the higher value of (C-12)O/(C-13)O found for the nightside mesosphere of Venus are offered.
Metastable O(1D) atoms may be quenched in collisions with ground state O(3P) atoms by transitions in the avoided crossing regions of the three lowest 3Pi(g) states of O2 of which the lowest separates to O(3P) + O(3P) and the two upper to O(3P) + O(1D). Quantal calculations of the adiabatic potential energy curves of the 3Pi(g) states are carried out with particular attention to an avoided crossing region in the lowest two states around a nuclear separation of 3.2a(0). Diabatic potential matrix elements are constructed from the adiabatic curves by imposing the requirement that they be smooth everywhere. A multi-state diabatic formulation is used to describe the scattering and the cross-sections for the collision-induced quenching of O(1D) atoms are calculated.